Increased demand of high purity metals for industrial growth and subsequently decline in metal reserves generates interest in exploring alternative sources for heavy metals. In view of maintaining sustainable development and following 3R’s principle recovery of metals from the secondary sector not only has an impact on the economy but also partly mitigates the problem of environment pollution due to metals. The present study is focus on the recovery of high grade cobalt using alkylphosphines extractant from cobalt acetate spent catalyst used in the manufacture of purified terephthalic acid (PTA) and dimethyl terephthalate (DMT). PTA and DMT are basic raw materials for polyethylene terephthalate (PET) used in to produce polyester fibres and synthetic textiles for packaging, PET bottles and recording tape. The proposed procedure gives high purity cobalt with almost a quantitative yield (~95%) and of course free from closely associated metals. The extractant could be regenerated and reused upto five cycles with no significant change in the extraction capability. The scaling up of investigated bench level cost effective methodology to the plant scale would certainly meet the growing demand of cobalt in making lithium-ion batteries as a result of the increase in demand of mobile phones, portable PCs and other electronic devices by urban population.